CN114931972B - High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application - Google Patents
High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application Download PDFInfo
- Publication number
- CN114931972B CN114931972B CN202210446248.5A CN202210446248A CN114931972B CN 114931972 B CN114931972 B CN 114931972B CN 202210446248 A CN202210446248 A CN 202210446248A CN 114931972 B CN114931972 B CN 114931972B
- Authority
- CN
- China
- Prior art keywords
- hbeta
- catalyst
- solid
- preparing
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000011973 solid acid Substances 0.000 claims abstract description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 125000005842 heteroatom Chemical group 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 16
- 230000001588 bifunctional effect Effects 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- -1 alkyl cycloalkanes Chemical class 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 239000012084 conversion product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a high-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, and relates to the field of industrial application catalyst preparation. The method comprises the following steps: preparation of silanized PHAPTMS gas phase SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Preparing a mesoporous Beta precursor; preparing an HBeta solid acid carrier; ni/Mo@HBeta catalyst is prepared. Also discloses the Ni/Mo@HBeta catalyst obtained by the method and application thereof. The invention adopts silanized PHAPHAPTMS gas phase SiO 2 As a silicon source for hydrothermal synthesis, preparing a mesoporous Beta precursor under a low-temperature hydrothermal condition, and then preparing an HBeta solid acid carrier by high-temperature roasting; aiming at the structure and alkali resistance of the HBeta solid acid carrier, the loaded non-noble metal cluster precipitate is uniformly dispersed in the surface and mesoporous pore canal of the HBeta solid acid carrier by a modified fractional deposition-precipitation method, and the Ni/Mo@HBeta catalyst is prepared by combining an oxidation-reduction modulation method, has high reaction activity, excellent heteroatom resistance and strong durability, and can efficiently hydrogenate saturated aromatic rings and simultaneously remove heteroatoms in the mild catalytic hydrogenation conversion reaction of bio-derived oil.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a high-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, a preparation method and application.
Background
The bio-derived oil is obtained by high-efficiency depolymerizing the biomass macromolecular network structure, hetero atoms in the bio-derived oil are removed by further adopting a high-activity catalyst, the hetero atoms are mainly O, N and S, saturated aromatic rings are hydrogenated, branched paraffins are isomerized to obtain naphthenes and isoparaffins, and the bio-derived oil is an important low-carbon energy process processing conversion path.
Based on the development of a large background of the energy industry and the actual demand of a biomass conversion process path, a high-activity bifunctional catalyst is developed, different types of heteroatom bridging bonds are efficiently broken and heteroatoms are removed in the reaction process through the cooperation of the catalytic performance of non-noble metals and solid acid carriers in a proper catalytic hydrogenation conversion system, and simultaneously, the isomerization of hydrogenated saturated aromatic ring cascade straight-chain alkane is a technical key of efficient clean conversion of biomass.
Therefore, research on a high-dispersity bimetallic cluster supported high-activity bifunctional catalyst is needed to realize efficient and clean conversion of biomass.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, a preparation method and application thereof, and adopts silanization PHAPTMS gas phase SiO 2 As a silicon source for hydrothermal synthesis, mesoporous Beta precursor is prepared under low-temperature hydrothermal condition, and then gradient ions are usedPreparing an HBeta solid acid carrier by high-temperature roasting in an exchange cascade nitrogen atmosphere furnace; aiming at the structure and alkali resistance of the HBeta solid acid carrier, the loaded non-noble metal cluster precipitate is uniformly dispersed in the surface and mesoporous pore canal of the HBeta solid acid carrier by a modified fractional deposition-precipitation method, and the Ni/Mo@HBeta catalyst is prepared by combining an oxidation-reduction modulation method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
according to a first aspect of an embodiment of the present invention, a method for preparing a high-dispersity Ni/Mo cluster-supported mesoporous Beta catalyst is provided.
In one embodiment, the method for preparing the high dispersity Ni/Mo cluster supported mesoporous Beta catalyst comprises the following steps:
preparation of silanized PHAPTMS gas phase SiO 2 ；
Preparing a mesoporous Beta precursor;
preparing an HBeta solid acid carrier;
Ni/Mo@HBeta catalyst is prepared.
Alternatively, preparing silanized PHAPHAPTMS gas phase SiO 2 The method comprises the following steps:
a1, siO in gas phase 2 :H 2 O:PHAPTMS:CH 3 OH is mixed according to the mol ratio of 1:60:0.1-0.2:6, and raw material mixed solution is obtained;
a2, heating the raw material mixed solution to 90 ℃, stirring under reflux, wherein the stirring speed is 50rad/min, the stirring time is 8h, and naturally cooling to room temperature to obtain a solid-liquid mixture, wherein the heating rate is 5 ℃/min;
a3, centrifuging the solid-liquid mixture to obtain a solid, washing the solid with methanol for 3 times at normal temperature, and then drying the solid in vacuum to obtain the silanized PHAPTMS gas-phase SiO 2 Wherein the drying temperature is 50 ℃ and the drying time is 10 hours.
Optionally, the step of preparing the mesoporous Beta precursor comprises:
b1, naOH: al 2 O 3 TEAbr, silanized PHAPTMS gas phase SiO 2 Placing the mixture in 18mL of deionized water according to the molar ratio of 12:450-500:3725:4280, sealing and stirring at normal temperature, wherein the stirring rate is 200rad/min, stirring for 2-3h to obtain gel;
b2, transferring the obtained gel into a self-generated pressure hydrothermal reaction kettle, sealing, crystallizing at 130-155 ℃ for 13-18 d to obtain a mixture, washing with water, and centrifuging to obtain a precipitate with pH of 7;
and b3, drying the obtained precipitate at 90 ℃ for 24 hours to obtain a dried precipitate, heating the dried precipitate to 500-600 ℃ in an oxygen atmosphere furnace for roasting for 4-7 hours, and cooling to room temperature to obtain the mesoporous Beta precursor, wherein the heating rate is 5-10 ℃/min.
Optionally, the step of preparing a mesoporous HBeta solid acid support comprises:
c1, placing the mesoporous Beta precursor in 1.0mol L -1 Ion exchange is carried out in the ammonium nitrate solution, the mixture is stirred for 1.2 hours at the temperature of 35 ℃ and the rotating speed of 100rad/min, and the precipitate is centrifugally collected after three times of ion exchange;
and c2, drying the obtained precipitate at 90 ℃ for 24 hours, placing the precipitate in an oxygen atmosphere furnace for roasting at 500-600 ℃ for 4-7 hours, and cooling to room temperature to obtain the HBeta solid acid carrier.
Optionally, the step of preparing the Ni/mo@hbeta catalyst comprises:
d1, mixing the HBeta solid acid carrier with deionized water according to a solid-to-liquid ratio of 1:25, placing in a closed container, heating to 45-65 ℃ under the stirring speed of 200rad/min, adding Ni salt and Mo salt, and maintaining for 45-65min;
d2, dropwise adding 2.5-3.5 wt% of dilute ammonia water into the closed container in the step d1 through a separating funnel until the pH value is 9.5-11, stirring, wherein the stirring speed is 200rad/min, the stirring time is 40-60min, separating precipitate and drying to obtain a Ni/Mo@HBeta precursor;
d3, placing the obtained Ni/Mo@HBeta precursor in an oxygen atmosphere furnace, heating to 200 ℃ for 0.8h, keeping the heating rate at 2 ℃/min, switching oxygen to hydrogen, heating to 480 ℃ at the same heating rate, keeping for 3h, and cooling to obtain the Ni/Mo@HBeta catalyst.
Optionally, in step a1, siO in the gas phase in the raw material proportion 2 The molar ratio to PHAPTMS is 1:0.12; the solid-to-liquid ratio of the solid and the methanol in the washing in the step a3 is 1:30, the washing time was 15min.
Optionally, in step b1, mesoporous Beta prepares raw material Al 2 O 3 With PHAPTMS gas phase SiO 2 The molar ratio of (2) is 480: 4280.
Optionally, in step b2, the crystallization temperature in the autogenous pressure hydrothermal reaction kettle is 135 ℃ and the crystallization time is 16d.
Optionally, in step b3, the temperature rising rate of the baking of the dried precipitate is 8 ℃/min, the baking temperature is 560 ℃ and the baking time is 5h.
Optionally, in step d1, the temperature of the closed container is 55 ℃, and after adding Ni salt and Mo salt, stirring is continued for 50min, wherein the sum of the Ni and Mo loading amounts is 3-13 wt%.
Optionally, in step d2, the concentration of the dilute ammonia water is 3.0wt%, the pH of the solution in the closed container is 10.6, and the stirring time is 55min.
According to a second aspect of embodiments of the present invention, a high dispersity Ni/Mo cluster supported mesoporous Beta (Ni/mo@hbeta) catalyst is presented.
According to a third aspect of embodiments of the present invention, there is provided the use of the above catalyst.
In one embodiment, the above catalyst is applied to the catalytic hydroconversion of bio-derived oils into paraffins and naphthenes.
The beneficial effects of the invention are as follows:
1. the invention adopts SiO 2 As a silicon source, the mesoporous Beta zeolite precursor with the aperture of 2-50 nm is successfully prepared in a low-temperature hydrothermal environment, and the HBeta formed after ion exchange has higher thermal and hydrothermal stability, high BET specific surface area, uniform through-channels in the structure and more uniform distribution of accessible acid sites.
2. According to the invention, the loaded Ni and Mo cluster precipitates are uniformly dispersed on the surface of the HBeta solid acid carrier and in the mesoporous pore canal by a modified fractional deposition-precipitation method, and the high-activity Ni/Mo@HBeta dual-function catalyst with active Ni and Mo components in a cluster form is obtained by combining an oxidation-reduction modulation method.
3. The high-activity Ni/Mo@HBeta bifunctional catalyst prepared by the invention controls d-orbit hole electrons to optimize the hydrogenation reaction activity of non-noble metals by optimizing the atomic distance between Ni and Mo clusters. Under the synergistic effect of Ni and Mo clusters and mesoporous HBeta, the bridging bond containing hetero atoms in the organic macromolecules in the bio-derived oil can be efficiently cracked and removed, the aromatic rings in the reaction system are efficiently hydrogenated and saturated, and the alkane is efficiently isomerized, and meanwhile, the poisoning and the inactivation of the Ni/Mo@HBeta bifunctional catalyst caused by the hetero atoms can be effectively avoided.
4. The Ni/Mo@HBeta bifunctional catalyst prepared by the invention is applied to a mild hydro-conversion system of bio-derived oil, wherein oxygen-containing compounds, nitrogen-containing compounds, sulfur-containing compounds and aromatic hydrocarbons in the bio-derived oil can be completely converted into 61.5wt% of alkyl cycloalkanes and 38.5wt% of alkane, and the generated alkyl cycloalkanes and alkane are high-quality base oils of special fuels and high-density fuels.
Drawings
FIG. 1 is a schematic diagram showing the N of a 10Ni/3Mo@HBeta bifunctional catalyst of example 1 of the present invention 2 -adsorption-desorption isotherm plot and pore size profile;
FIG. 2 is an SEM image of a 10Ni/3Mo@HBeta bifunctional catalyst of example 1 of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the high-dispersity Ni/Mo cluster supported mesoporous Beta catalyst comprises the following steps:
1. 10g of gas phase SiO 2 Dissolving in 180mL deionized water, then 32.0mL CH was added 3 OH and 32.4g of PHAPTMS are heated to 90 ℃ at a speed of 5 ℃/min, stirred under reflux condition, the stirring speed is 50rad/min, the stirring time is 8h, then naturally cooled to room temperature to obtain a solid-liquid mixture, the solid obtained by centrifuging the solid-liquid mixture is washed by methanol for 3 times and then vacuum-dried, the drying temperature is 50 ℃ and the drying time is 10h to obtain the silanized PHAPTMS gas phase SiO 2 Wherein the solid-to-liquid ratio of the solid to the methanol is 1:30, the washing time is 15min;
2. 0.02g NaOH and 0.49g NaAlO are added in sequence 2 3.73g TEAbr, 4.28g silanized PHAPTMS gas phase SiO 2 Adding the gel into 18mL of deionized water under normal temperature stirring, wherein the stirring speed is 200rad/min, and the stirring time is 2h, so as to obtain gel; transferring the obtained gel into a self-generated pressure hydrothermal reaction kettle, sealing, crystallizing at 135 ℃ for 16d to obtain a mixture, washing with water, and centrifuging to obtain a precipitate with pH of 7; drying the obtained precipitate at 90 ℃ for 24 hours to obtain a dried precipitate, heating the dried precipitate to 560 ℃ in an oxygen atmosphere furnace for roasting for 5 hours, and cooling to room temperature to obtain a mesoporous Beta precursor, wherein the heating rate is 8 ℃/min; because the alumina with chemical activity is not present, sodium metaaluminate is selected in the reaction process;
3. the mesoporous Beta precursor was placed at 1.0mol L -1 Ion exchange is carried out in the ammonium nitrate solution, the mixture is stirred for 1.2 hours at the temperature of 35 ℃ and the rotating speed of 100rad/min, and the precipitate is centrifugally collected after three times of ion exchange; drying the obtained precipitate at 90 ℃ for 24 hours to obtain an ammonium mesoporous Beta precursor; placing an ammonium type mesoporous Beta precursor in an oxygen atmosphere muffle furnace for roasting at 560 ℃ for 5 hours, and cooling to room temperature to obtain a mesoporous HBeta solid acid carrier;
4. mixing 4g mesoporous HBeta solid acid carrier with 100mL deionized water, placing in a closed container, heating to 55deg.C at a rotation speed of 200rad/min, and adding 2.04g Ni (NO) 3 ) 2 ·6H 2 O and 0.24g (NH) 4 ) 6 MoO 24 ·4H 2 Sealing and stirring for 50min after O; dropwise adding dilute ammonia water with the concentration of 3.0wt% into a closed container through a separating funnel until the pH value is 10.6, stirring, wherein the stirring speed is 200rad/min, and after the stirring time is 55min, separating and drying a precipitate to obtain a Ni/Mo@HBeta precursor; and (3) placing the Ni/Mo@HBeta precursor in an oxygen atmosphere furnace, heating to 200 ℃ at a speed of 2 ℃/min, maintaining for 0.8h, switching the oxygen atmosphere to be a hydrogen atmosphere, heating to 480 ℃ at a speed of 2 ℃/min, maintaining at a constant temperature for 3h, and cooling to obtain the 10Ni/3Mo@HBeta catalyst.
FIG. 1 is N of a Ni/Mo@HBeta bifunctional catalyst 2 The adsorption-desorption isotherm curves and pore size distribution diagrams, it can be seen from fig. 1 that the Ni/mo@hbeta bifunctional catalyst has mesoporous channels of 2-5 nm; fig. 2 is an SEM image of a Ni/mo@hbeta bifunctional catalyst, and from fig. 2, it is known that metal Ni/Mo is uniformly dispersed on the surface of an HBeta acidic carrier and exists in a cluster form with high dispersity, and the higher the dispersity of the catalyst, the higher the atom utilization efficiency and the better the catalytic performance.
Example 2
The difference from example 1 is that: non-noble metal salt Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 ) 6 MoO 24 ·4H 2 The addition amount of O is 0.80g and 0.20g respectively, and the prepared bifunctional catalyst is 8Ni/5Mo@HBeta-1.
Example 3
The difference from example 1 is that: non-noble metal salt Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 ) 6 MoO 24 ·4H 2 The addition amount of O is 0.50g and 0.30g respectively, and the prepared bifunctional catalyst is 5Ni/8Mo@HBeta-2.
Example 4
The difference from example 1 is that: non-noble metal salt Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 ) 6 MoO 24 ·4H 2 The addition amount of O is 0.30g and 1.00g respectively, and the prepared bifunctional catalyst is 3Ni/10Mo@HBeta-3.
Example 5
The difference from example 1 is that the non-noble metal salt Ni #NO 3 ) 2 ·6H 2 The addition amount of O is 1.30g, and the prepared bifunctional catalyst is 13Ni@HBeta.
Example 6
Unlike example 1, the non-noble metal salt (NH 4 ) 6 MoO 24 ·4H 2 The addition amount of O is 1.30g, and the prepared bifunctional catalyst is 13Mo@HBeta.
Application example 1
The catalysts prepared in examples 1 to 6 were applied to catalytic hydroconversion of the model compound of bio-derived oil (4-methoxyphenol).
Reaction conditions: the catalysts were evaluated in a programmed temperature-controlled autoclave with mechanical stirring.
Taking 4-methoxyphenol as a model compound, and sequentially adding 0.05g of catalyst, 1mL of 4-methoxyphenol and 20mL of n-hexane into a miniature high-pressure reaction kettle, wherein the reaction conditions are as follows: the initial hydrogen pressure was 5Mpa, the reaction temperature was 140℃and the reaction time was 2h. The catalysts of examples 1 to 6 were evaluated for their catalytic hydroconversion ability.
The analysis method of the hydrogenation products comprises the following steps: the organic molecular composition of the catalytic hydrogenation conversion product is analyzed by adopting an Agilent 8890/5977 quadrupole gas chromatograph/mass spectrometer, the chromatographic column is an HP-5MS capillary cross-linked column with the diameter of 60m multiplied by 0.25mm multiplied by 0.25 mu m, and the database is an NIST20 database.
The 6 kinds of energy catalysts prepared in examples 1 to 6 were subjected to catalytic hydroconversion performance evaluation of 4-methoxyphenol under the same conditions at different times to obtain conversion of 4-methoxyphenol and molar yields of the products as shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, in the catalytic hydroconversion evaluation of the model compound 4-methoxyphenol, ni@HBeta and Mo@HBeta loaded with a single metal, ni/Mo@HBeta can fully convert 4-methoxyphenol into cyclohexane as compared with Ni/Mo@HBeta loaded with a double metalAlkane and metal Mo are introduced, so that the electron efficiency is enhanced, the service life of the catalyst is prolonged, and the bimetallic catalyst has more advantages. Compared with different loading amounts, the catalyst Ni/Mo@HBeta loaded with Ni and Mo with different amounts of non-noble metals has more advantages and can be completely fractured>C ar O bridge bond, removing oxygen atom in 4-methoxy phenol, and can completely saturate benzene ring to cyclohexane.
Application example 2
The Ni/Mo@HBeta catalyst prepared in example 1 is applied to a biological derived oil catalytic hydroconversion reaction.
Reaction conditions: the catalysts were evaluated in a programmed temperature-controlled autoclave with mechanical stirring.
0.1g of bio-derived oil is taken as a reaction substrate, 0.05g of Ni/Mo@HBeta catalyst and 20mL of normal hexane solvent are placed in a miniature high-pressure reaction kettle, and the reaction conditions are as follows: the initial hydrogen pressure was 5Mpa, the reaction temperature was 140℃and the reaction time was 2h. The catalytic hydroconversion performance of the Ni/Mo@HBeta catalyst of example 1 was evaluated.
The analysis method of the hydrogenation products comprises the following steps: the organic molecular composition of the catalytic hydrogenation conversion product is analyzed by adopting an Agilent 8890/5977 quadrupole gas chromatograph/mass spectrometer, the chromatographic column is an HP-5MS capillary cross-linked column with the diameter of 60m multiplied by 0.25mm multiplied by 0.25 mu m, and the database is an NIST20 database.
The Ni/Mo@HBeta catalyst prepared in example 1 was quantitatively analyzed by GC/MS for bio-derived oil and high value base fuel oil organic group components, and the content of each group component is shown in Table 2.
TABLE 2
Application example 2 shows that the Ni/Mo@HBeta catalyst can fully convert aromatic hydrocarbon, oxygen-containing compound, nitrogen-containing compound and sulfur-containing compound in bio-derived oil into alkane and alkyl cycloalkane in the catalytic hydroconversion reaction of the bio-derived oil, and the hydroconversion product is high-quality base oil of special fuel and high-density fuel. In addition, the catalyst is more advantageous in terms of price than a noble metal catalyst in that non-noble metals Ni and Mo are supported on mesoporous HBeta in a cluster form.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (3)
1. The preparation method of the mesoporous Beta catalyst loaded by the Ni/Mo clusters with high dispersity is characterized by comprising the following steps:
preparation of silanized PHAPTMS gas phase SiO 2 ；
Preparing a mesoporous Beta precursor;
preparing an HBeta solid acid carrier;
preparing a Ni/Mo@HBeta catalyst;
the preparation of the silanized PHAPTMS gas phase SiO 2 The method comprises the following steps:
a1, siO in gas phase 2 :H 2 O:PHAPTMS:CH 3 OH is mixed according to the mol ratio of 1:60:0.1-0.2:6, and raw material mixed solution is obtained;
a2, heating the raw material mixed solution to 90 ℃, stirring under reflux, wherein the stirring speed is 50rad/min, the stirring time is 8h, and naturally cooling to room temperature to obtain a solid-liquid mixture, wherein the heating rate is 5 ℃/min;
a3, centrifuging the solid-liquid mixture to obtain a solid, washing the solid with methanol for 3 times at normal temperature, and then drying the solid in vacuum to obtain the silanized PHAPTMS gas-phase SiO 2 Wherein the drying temperature is 50 ℃ and the drying time is 10 hours;
the step of preparing a mesoporous Beta precursor comprises:
b1, naOH: al 2 O 3 TEAbr, silanized PHAPTMS gas phase SiO 2 Placing the gel in 18mL of deionized water according to the molar ratio of 12:450-500:3725:4280, sealing and stirring at normal temperature, wherein the stirring speed is 200rad/min, and the stirring time is 2-3h, so as to obtain gel;
b2, transferring the obtained gel into a self-generated pressure hydrothermal reaction kettle, sealing, crystallizing at 130-155 ℃ for 13-18 d to obtain a mixture, washing with water, and centrifuging to obtain a precipitate with pH of 7;
b3, drying the obtained precipitate at 90 ℃ for 24 hours to obtain a dried precipitate, heating the dried precipitate to 500-600 ℃ in an oxygen atmosphere furnace for roasting for 4-7 hours, and cooling to room temperature to obtain a mesoporous Beta precursor, wherein the heating rate is 5-10 ℃/min;
the step of preparing the HBeta solid acid carrier comprises the following steps:
c1, placing the mesoporous Beta precursor in 1.0mol L -1 Ion exchange is carried out in the ammonium nitrate solution, the mixture is stirred for 1.2 hours at the temperature of 35 ℃ and the rotating speed of 100rad/min, and the precipitate is centrifugally collected after three times of ion exchange;
c2, drying the obtained precipitate at 90 ℃ for 24 hours, placing the precipitate in an oxygen atmosphere furnace for roasting at 500-600 ℃ for 4-7 hours, and cooling to room temperature to obtain the HBeta solid acid carrier;
the preparation method of the Ni/Mo@HBeta catalyst comprises the following steps:
d1, mixing the HBeta solid acid carrier with deionized water according to a solid-to-liquid ratio of 1:25, placing in a closed container, heating to 45-65 ℃ at a rotating speed of 200rad/min, adding Ni salt and Mo salt, and continuing stirring for 45-65min;
d2, dropwise adding dilute ammonia water into the closed container in the step d1 until the pH value is 9.5-11, stirring, wherein the stirring speed is 200rad/min, the stirring time is 40-60min, separating and drying a precipitate to obtain a Ni/Mo@HBeta precursor;
d3, placing the obtained Ni/Mo@HBeta precursor in an oxygen atmosphere furnace, heating to 200 ℃ for 0.8h, keeping the heating rate at 2 ℃/min, switching oxygen to hydrogen, heating to 480 ℃ at the heating rate of 2 ℃/min, keeping for 3h, and cooling to obtain the Ni/Mo@HBeta catalyst;
in step a1, gas phase SiO in the raw material proportion 2 The molar ratio to PHAPTMS is 1:0.12; the solid-to-liquid ratio of the solid and the methanol in the washing in the step a3 is 1:30, the washing time is 15min;
in step b1, al 2 O 3 With silanized PHAPTMS gas phase SiO 2 The molar ratio of (2) is 480:4280;
in step d1, the sum of Ni and Mo loadings was 13wt%.
2. A Ni/mo@hbeta catalyst prepared by the method of claim 1.
3. The use of a Ni/mo@hbeta catalyst according to claim 2, wherein said Ni/mo@hbeta catalyst is applied to catalytic hydroconversion of bio-derived oils into paraffins and naphthenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210446248.5A CN114931972B (en) | 2022-04-26 | 2022-04-26 | High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210446248.5A CN114931972B (en) | 2022-04-26 | 2022-04-26 | High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114931972A CN114931972A (en) | 2022-08-23 |
| CN114931972B true CN114931972B (en) | 2023-10-24 |
Family
ID=82863248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210446248.5A Active CN114931972B (en) | 2022-04-26 | 2022-04-26 | High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114931972B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075459A (en) * | 2002-08-19 | 2004-03-11 | Tokuyama Corp | Modified silica dispersion and method for producing the same |
| CN107804856A (en) * | 2017-12-13 | 2018-03-16 | 山东齐鲁华信高科有限公司 | The direct synthesis method of high silica alumina ratio Beta molecular sieves |
| CN108043455A (en) * | 2017-12-06 | 2018-05-18 | 浙江海洋大学 | For synthesizing solid acid catalyst of seven ring of dioxy and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy |
| KR20210066563A (en) * | 2019-11-28 | 2021-06-07 | 창원대학교 산학협력단 | A method of surface modification of SiO2 with silane coupling agent |
| CN113164934A (en) * | 2018-12-03 | 2021-07-23 | 国立大学法人北海道大学 | Functional structure |
| CN113164938A (en) * | 2018-12-03 | 2021-07-23 | 古河电气工业株式会社 | Catalyst structure, method for producing same, and method for producing hydrocarbon using same |
-
2022
- 2022-04-26 CN CN202210446248.5A patent/CN114931972B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075459A (en) * | 2002-08-19 | 2004-03-11 | Tokuyama Corp | Modified silica dispersion and method for producing the same |
| CN108043455A (en) * | 2017-12-06 | 2018-05-18 | 浙江海洋大学 | For synthesizing solid acid catalyst of seven ring of dioxy and preparation method thereof and the method using solid acid catalyst synthesis seven ring of dioxy |
| CN107804856A (en) * | 2017-12-13 | 2018-03-16 | 山东齐鲁华信高科有限公司 | The direct synthesis method of high silica alumina ratio Beta molecular sieves |
| CN113164934A (en) * | 2018-12-03 | 2021-07-23 | 国立大学法人北海道大学 | Functional structure |
| CN113164938A (en) * | 2018-12-03 | 2021-07-23 | 古河电气工业株式会社 | Catalyst structure, method for producing same, and method for producing hydrocarbon using same |
| KR20210066563A (en) * | 2019-11-28 | 2021-06-07 | 창원대학교 산학협력단 | A method of surface modification of SiO2 with silane coupling agent |
Non-Patent Citations (1)
| Title |
|---|
| "Mo/HBeta催化剂二苯并噻加氢脱硫性能研究";吴永进;《中国优秀硕士学位论文全文数据库 工程科技I辑》;13-15、29-34 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114931972A (en) | 2022-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Creyghton et al. | Vapour-phase hydrodehalogenation of chlorobenzene over platinum/H-BEA zeolite | |
| CN109731608A (en) | A kind of bifunctional catalyst and preparation method thereof without sodium Si-Al molecular sieve of package metals nano particle | |
| CN102698788B (en) | High-dispersion dual-functional catalyst for hydrogenating and deoxidizing phenol and preparation method of catalyst | |
| CN110935473B (en) | Hydrodeoxygenation catalyst and preparation method and application thereof | |
| CN109772432A (en) | A kind of benzene selective hydrogenation alkylation prepares cyclohexyl benzene metallic cover type catalyst and preparation method thereof, application method | |
| CN110201711B (en) | Catalyst for synthesizing low-carbon mixed alcohol by carbon dioxide hydrogenation and preparation method thereof | |
| CN114931972B (en) | High-dispersity Ni/Mo cluster supported mesoporous Beta catalyst, preparation method and application | |
| CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN101920199A (en) | Fischer-Tropsch synthesis cobalt-based catalyst using modified silica gel as carrier and preparation method thereof | |
| CN109046442B (en) | Hierarchical pore molecular sieve supported platinum-iron bimetallic catalyst and preparation and application thereof | |
| CN111111649A (en) | Heteroatom-modified Pd nano catalytic material and preparation method and application thereof | |
| CN114931971B (en) | Nickel nanocluster loaded intergranular mesoporous zeolite catalyst and preparation method and application thereof | |
| CN112642417B (en) | Preparation method and application of dehydrogenation catalyst carrier | |
| Xu et al. | Partial hydrogenation of anisole to cyclohexanone in water medium catalyzed by atomically dispersed Pd anchored in the micropores of zeolite | |
| CN109174159B (en) | Fixed-point deuterium adding photocatalyst | |
| CN107008489B (en) | Molecular sieve supported vanadium-based catalyst for lignin hydrogenation depolymerization and preparation method thereof | |
| CN111389453B (en) | Method for converting high-concentration lignin into cycloparaffin by liquid phase | |
| CN112979406B (en) | Method for catalyzing alpha-pinene dimerization-hydrogenation reaction by bifunctional microporous molecular sieve | |
| CN112058306B (en) | High-activity supported bifunctional catalyst, preparation method and application thereof | |
| CN112058304B (en) | Dual-function catalyst capable of adjusting solid acidity, preparation method and application thereof | |
| CN112439444B (en) | Preparation method and application of supported hierarchical pore solid acid bifunctional catalyst | |
| JP2023533579A (en) | Process for preparing copper-based hydrogenation catalysts, catalysts prepared therewith and uses | |
| CN1306885A (en) | Method of synthesizing medium-pore holecular sieve MCM-41 and preparing hydrogenatino and desulfurization catalyst with MCM-41 as carrier | |
| CN115608361B (en) | Catalyst for reductive amination and preparation method and application thereof | |
| CN113893871B (en) | Preparation method of nitrogen-doped high-dispersivity cobalt catalyst for preparing second-generation biodiesel by oil hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |